Cohesive assembly of carbon and its application

ABSTRACT

Cohesive carbon assemblies are prepared by obtaining a carbon starting material in the form of powder, particles, flakes, or loose agglomerates, dispersing the carbon in a selected organic solvent by mechanical mixing and/or sonication, and substantially removing the organic solvent, typically by evaporation, whereby the cohesive assembly of carbon is formed. The method is suitable for preparing free-standing, monolithic assemblies of carbon nanotubes in the form of films, wafers, or discs, having high carbon packing density and low electrical resistivity. The method is suitable for preparing adherent cohesive carbon assemblies on substrates comprising various materials. The assemblies have various potential applications, such as electrodes or current collectors in electrochemical capacitors, fuel cells, and batteries, or as electromagnetic interference shielding materials.

This application is a continuation of PCT/US2012/042956, filed Jun. 18,2012; which claims the priority of U.S. Provisional Application Nos.61/499,084, filed Jun. 20, 2011, and 61/500,862, filed Jun. 24, 2011.The contents of the above-identified applications are incorporatedherein by reference in their entireties.

TECHNICAL FIELD

This invention relates to a cohesive assembly of carbon, and to methodsfor preparing a cohesive assembly of carbon, in which the startingcarbon materials, under certain prescribed conditions, self-assembleinto a disc, wafer, film, or other object of a desired shape. Inpreferred embodiments, the carbon assembly prepared by the inventedmethod comprises carbon nanotubes. The prepared assembly shows goodmechanical strength and integrity, high carbon packing density, highsurface area, and low electrical resistivity, and has various potentialapplications such as in electrical power storage and electromagneticinterference shielding. The cohesive assembly of carbon is especiallyuseful as an electrode or a current collector for an electrochemicalcapacitor, fuel cell, or battery.

BACKGROUND

Assemblies of carbon, derived from a variety of carbon sources, have amultitude of current and anticipated commercial, industrial, andhigh-technology applications. For example, activated charcoal oractivated carbon, which is usually in the form of loose powder,particles, or irregular agglomerates, has a variety of uses infiltration and catalyst support. This material has also recently beenapplied to energy storage applications, as an ionic exchange medium orcapacitor electrode material. Graphite in its various forms has numeroususes, for example, as refractory material, in brake linings, and aselectrodes in electric arc furnaces. Intercalated graphite and expandedgraphite have been studied for use as fire retardants and hightemperature applications. These cohesive carbon assemblies have manydesirable properties such as resistance to chemical attack, resistanceto high temperatures, and high surface area in the case of activatedcarbon, and electrical conductivity and lubricity in the case ofgraphite. However, these materials typically require a binder or matrixmaterial to form them into an assembly of a desired shape and size,having good mechanical strength and integrity.

More recently, assemblies of carbon nanotubes (CNTs) in various formshave attracted much attention and are being explored and developed fordiverse applications. Such assemblies have been referred to in theliterature as “buckypaper” or “buckydiscs”. For example, Dharap et al in“Nanotube film based on single-wall carbon nanotubes for strainsensing”, Nanotechnology 15 (2004), pp. 379-382, investigate the use ofisotropic films of randomly oriented CNTs as mechanical strain sensors.Cao et al, in “Random networks and aligned arrays of single-walledcarbon nanotubes for electronic device applications,” Nano Research 1, 4(2008), pp. 259-272, discuss the use of random networks or alignedarrays of CNTs as thin-film transistors. Ma et al, in “Methods of makingcarbide and oxycarbide containing catalysts,” U.S. Pat. No. 7,576,027B2, disclose catalyst supports for fluid phase chemical reactions madefrom randomly entangled CNT aggregates. And Liu et al, in“Electrochemical capacitor with carbon nanotubes,” U.S. PatentApplication Publication US 2009/0116171 A1, disclose electrolyticcapacitors having electrodes made from free-standing CNT films.

Smalley et al in “Method for producing self-assembled objects comprisingsingle-wall carbon nanotubes and compositions thereof,” U.S. Pat. No.7,048,999 B2, disclose CNT assemblies formed by a complex process of CNTend-cap removal and derivatization. The buckypaper disclosed therein isa loosely assembled CNT felt or mat that is supported on a substrate.Other structures disclosed therein such as molecular arrays andself-assembled monolayers are described as requiring a substrate ormatrix material such as a resin, metal, ceramic, or cermet. Furthermore,the self-assembled structures disclosed therein comprise functionalagents to bond the CNTs together, which may adversely affect thestructures' electrical properties.

Tohji et al in “Carbon nanotubes aggregate, method for forming same, andbiocompatible material,” U.S. Patent Application Publication US2007/0209093 A1, disclose a method for CNT aggregate formation involvingexposure to fluorine gas followed by sintering at high temperature andpressure. The aggregates are characterized as being fragile.

Liu et al in US 2009/0116171 A1, and Hata et al in “Aligned carbonnanotube bulk aggregates, process for production of the same and usesthereof,” U.S. Patent Application Publication US 2009/0272935 A1,disclose methods for preparing CNT assemblies that require the use ofCNT forests grown by CVD processes on a substrate. These methods involvea sequence of solvent washing, pressing, and/or drying steps and arelimited to the scale of the starting CNT forest. Furthermore, theseassemblies are characterized by a predominant orientation or alignmentof the CNTs, which imparts the assembly with anisotropic and largelyunidirectional properties.

Whitby et al in “Geometric control and tuneable pore size distributionof buckypaper and bucky discs,” Carbon 46 (2008) pp. 949-956, disclose afrit compression method for forming CNT assemblies, which also requireshigh pressures. Also, the CNTs are not uniformly distributed within theassemblies, and the assemblies have large macropores and very highporosity (>80%).

A method to form a solution of single-walled CNTs in sulfuricsuper-acids is disclosed by Davis et al in “Phase Behavior and Rheologyof SWNTs in Superacids,” Macromolecules 37 (2004) pp. 154-160. A methodis also disclosed to produce an entangled mat of CNT ropes by quenchingin ether and filtering.

R. Signorelli et al in “High Energy and Power Density NanotubeUltracapacitor Design, Modeling, Testing and Predicted Performance,”presented at The 19th International Seminar on Double Layer Capacitorsand Hybrid Energy Storage Devices (Dec. 7-9, 2009, Deerfield Beach,Fla., USA), and in “Electrochemical Double-Layer Capacitors Using CarbonNanotube Electrode Structures,” Proceedings of the IEEE 97, 11(2009),pp. 1837-1847, disclose vertically aligned single-walled CNT (SWCNT) andmulti-walled CNT (MWCNT) “forest”-type assemblies intended for use asbinder-free electrodes. These assemblies, however, show low bulk densityof 0.45 g/cm³ or less (0.1 g/cm³ in the case of SWCNT), requiring animpractically high volume of material for adequate capacitorperformance. Scalability of these CNT forests for manufacturing purposesis questionable, and they have inferior mechanical properties for use ascurrent collectors.

A similar forest-type assembly produced from double-walled CNT (DWCNT),intended for use as a capacitor electrode, is disclosed by T. Asari in“Electric Double-Layer Capacitor Using Carbon Nanotubes Grown Directlyon Aluminum”, presented at ICAC2010, The 2010 International Conferenceon Advanced Capacitors (May 31-Jun. 2, 2010, Kyoto, Japan). Thisassembly has similar drawbacks as that of Signorelli; namely, lowdensity, non-scalability, and inferior mechanical properties.

A. Izadi-Najafabadi et al, in “Extracting the Full Potential ofSingle-Walled Carbon Nanotubes as Durable Supercapacitor ElectrodesOperable at 4 V with High Power and Energy Density,” in AdvancedMaterials, n/a. doi: 10.1002/adma.200904349 (Published on-line June 18,2010), describe a capacitor electrode based on a high-purity SWCNTforest processed into a binder-free assembly. This assembly showsattractive electronic performance characteristics as an electrode whentested under laboratory conditions. However, a sealed capacitor devicecould not be produced using this assembly due to excessive swelling whenimpregnated with the liquid electrolyte, indicating that the assemblyhad inferior mechanical strength and integrity.

There is interest in applying CNT technology to electrochemicaldouble-layer capacitors (EDLC), sometimes referred to as“supercapacitors” or “ultracapacitors”. This capacitor type has powerdensity somewhat lower than, but nearly approaching, that of standardcapacitors, but much higher energy density, approaching that of standardbatteries. EDLCs have many applications in consumer electronics, and areattractive for use in hybrid gas-electric vehicles and all-electricvehicles. Activated carbon is the most common material currently used aselectrodes in EDLCs. However, its performance may be reaching itstechnological limit and materials capable of higher energy and powerdensities are desired, especially for vehicle applications.

Lithium-ion is one battery type of particular interest for applicationof carbon nanotubes. Modern Li-ion batteries typically comprise acarbon-based anode, a cathode comprising an oxide such as LiCoO₂,LiFePO₄, LiNiCoAlO₂, or the like, and an electrolyte comprising alithium salt in an organic solvent. Li-ion batteries are commonly usedin consumer electronics, and are attractive for use in hybridgas-electric and all-electric vehicles. However, improvements in batteryperformance are needed for widespread vehicle application. Specifically,increased energy density, power density, lighter weight, and betterreliability are desirable. Particularly attractive are thinner and/orlighter electrode materials having lower electrical resistance, moreefficient ion transfer capability, and sufficient mechanical strengthfor battery use.

In a standard fuel cell, hydrogen is combined with oxygen to generateelectric current and water as a by-product. One fuel cell type ofcurrent high interest is the proton exchange membrane or polymerelectrolyte membrane (PEM) fuel cell. This design comprises a membraneelectrode assembly (MEA), which in turn comprises a center protonexchange membrane (PEM), and an electrode on either side of the PEM.Each electrode comprises a catalyst layer and a gas diffusion layer(GDL). The catalyst layer is typically comprised of fine metal particlesor powder (platinum for the anode, often nickel for the cathode) on aporous support material such as pressed carbon black. The GDL layer,which contacts the metallic current collector on the face opposite thecatalyst layer, is usually comprised of carbon paper or carbon cloth. Asin the case of Li-ion batteries, improvements in PEM fuel cellperformance are also needed for widespread application, especially invehicles. Stronger and more lightweight materials, having goodelectrical conductivity and providing more efficient electrochemicalreactions, are desirable for use as electrode materials, as either thecatalyst support and/or the GDL.

In various energy storage devices, including capacitors, fuel cells, andbatteries, a current collector comprising a metal plate is typicallyattached to the exposed (outward-facing) surface of the electrode, tocollect the current generated by the device and conduct it towards themachine or equipment that the device is powering. Aluminum and copperare typical metals used as current collectors. It is desirable that theweight and complexity of the energy storage devices be reduced, and onesuch approach is to combine the function of the electrode with that ofthe current collector in a single material. This may only beaccomplished if both the conductivity and mechanical strength andintegrity of the material are near enough to those of traditionalcurrent collectors, such that the performance of the device is notdiminished. In fact, enhancement of the device performance by using acombined electrode/current collector would be ideal.

WO 2010/102250 discloses preparing cohesive carbon assembly bydispersing carbon in a liquid halogen (e.g. bromine), followed bysubstantial removal of the liquid. However, bromine is highly toxic andexpensive. Bromine is also highly corrosive to most metals,significantly reducing its utility as a dispersing medium, since nocommon metal container or metal surface may come in contact with adispersion of carbon in a halogen-based liquid.

Therefore, there exists a need for a method for preparing a cohesivecarbon assembly that can avoid using the corrosive and toxic halogensolvents.

SUMMARY OF THE INVENTION

The present invention is directed to a method of preparing a cohesivecarbon assembly comprising: (a) obtaining a carbon starting material ina form of powder, particles, flakes, or loose agglomerates; (b)dispersing the carbon starting material in a selected organic solvent ina prescribed ratio to form a dispersion; and (c) substantially removingthe organic solvent in a controlled manner; whereby the cohesive carbonassembly is formed.

The present invention is also directed to a cohesive carbon assemblyprepared by the method described above, wherein the assembly is adherentto a metallic substrate.

The present invention is further directed to applications of thecohesive carbon assembly in, e.g. .electrical power storage andelectromagnetic interference shielding. The cohesive carbon assembly mayalso be used as an electrode and/or a current collector in a capacitor,fuel cell, or battery.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an optical image of a self-delaminating and self-standingcohesive assembly comprising single-walled carbon nanotubes (SWCNTs)prepared according to Example 2.

FIG. 2 is an optical image of a cohesive carbon assembly comprisingSWCNTs prepared according to Example 3.

FIG. 3 is a chart showing Raman spectra of as-received SWCNT powder, andthe top side and bottom side of a cohesive carbon assembly comprisingSWCNTs.

FIG. 4 is a set of two scanning electron microscope (SEM) images showinga top view (top) and a cross-sectional view bottom of a cohesive carbonassembly comprising SWCNTs.

FIG. 5 is an optical image of a set of five self-delaminating andself-standing cohesive assemblies comprising SWCNTs, 9 cm in diameter,prepared according to Example 11.

FIG. 6 is a SEM image showing a cross-sectional view of a self-standingcohesive assembly of SWCNTs prepared according to Example 11.

FIG. 7 is a schematic diagram showing the method for producing acohesive, adherent film comprising SWCNT on an aluminum substrate.

FIG. 8 is a pair of optical images showing two cohesive, adherent, SWCNTfilms on aluminum foil substrates, each 9 cm in diameter. The top imageshows the SWCNT films. The bottom image shows the aluminum foilsubstrates.

FIG. 9 is an optical image of a cohesive, adherent SWCNT film, 9 cm indiameter, on an aluminum foil substrate, showing the SWCNT film on oneside and the aluminum substrate on the other side.

FIG. 10 is a chart showing plots of imaginary impedance versus realimpedance (known as Nyquist plots), for an adherent cohesive SWCNTassembly formed on aluminum foil, and a free-standing cohesive SWCNTassembly.

DETAILED DESCRIPTION OF THE INVENTION

One aspect of the invention relates to a method of preparing a cohesivecarbon assembly. The method comprises: (a) obtaining a carbon startingmaterial in a form of powder, particles, flakes, or loose agglomerates;(b) dispersing the carbon starting material in an organic solvent in aprescribed ratio to form dispersion; and (c) substantially removing theorganic solvent in a controlled manner; whereby the cohesive carbonassembly is formed.

A cohesive assembly is defined herein as a self-assembled monolithicstructure in which the carbon is uniformly distributed; the cohesiveassembly has a distinct shape and size that is free-standing. Thecohesive assembly is further defined in that it does not adhere to anyother material or surface, has sufficient mechanical strength andintegrity that it does not require mechanical support by any othermaterial, nor does it require the presence of a binder material toretain its strength and integrity. It also can be moved from place toplace while retaining its structure, shape, and size. The cohesiveassembly shows no particular orientation or alignment of the individualunits of carbon of which it is comprised, and shows no unidirectional ororiented mechanical or electrical behavior.

The cohesive assembly is self-assembled in that, once the carbon in itsinitial form as described above is completely dispersed in a liquidmedium, no additional chemical modifications, physical alterations, ormechanical forces are applied to the carbon in order to form thecohesive assembly.

The carbon starting material comprises a carbon material selected fromthe group consisting of carbon nanotubes (CNTs, e.g. SWCNTs,double-walled carbon nanotubes (DWCNTs), and multi-walled carbonnanotubes (MWCNTs)), graphene, graphite, expanded graphite, exfoliatedgraphite, amorphous carbon, and any combinations thereof. In oneembodiment, the carbon starting material comprises SWCNTs.

In one embodiment, the carbon starting material is obtained in a form ofpowder, particles, flakes, loose agglomerates, or any appropriate formsthat can be dispersed in the organic solvent. In another embodiment, thecarbon starting material may be ground, pulverized, or mechanicallyaltered in one or more standard techniques to obtain the carbon startingmaterial in an appropriate form before being dispersed in the organicsolvent. For example, CNTs may be purchased from a commercial source,such as SWCNTs available from Thomas Swan and Co., Ltd (Consett, CountyDurham, United Kingdom) under the product name “Elicarb SW.” Thismaterial is supplied in the form of wetcake (loose agglomerates in anaqueous mixture) or as dry particles. The dry particles, which aretypically smaller than 5 mm in the largest dimension, may be usedas-received in the preparation of the cohesive carbon assemblies.Optionally, this material may be ground into smaller particles or powderand then used in the preparation of the cohesive carbon assemblies. Thewetcake material may be dried by any standard method, then mechanicallybroken apart into particles or loose agglomerates, and then used in thepreparation of the cohesive carbon assemblies. Optionally the driedwetcake material may be further ground into smaller particles or powder,and then used in the preparation of the cohesive carbon assemblies.Generally speaking, the powder, particles, flakes, or loose agglomeratesof carbon used in the invented method are smaller than 1 cm in thelargest dimension, preferably smaller than 3 mm in the largestdimension, and more preferably smaller than 1 mm in the largestdimension.

The organic solvent used in the method may be a substantially pureorganic compound or a mixture of more than one organic compound.Suitable organic solvents include, but are not limited to, toluene,o-dichlorobenzene (ODCB), isopropyl alcohol (IPA), N,N-dimethylformamide(DMF), substituted or unsubstituted benzene, chlorobenzene,m-dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene,m-dibromobenzene, o-dibromobenzene, toluene, o-xylene, m-xylene,p-xylene, 1,2-dichloroethane, 1,2-dibromoethane, chloroform, primaryamines, secondary amines, tertiary amines, dimethyl sulfoxide, and anycombinations thereof.

Preferably, the organic solvent is selected from the group consisting oftoluene, ODCB, IPA, DMF, and any combinations thereof. More preferably,the organic solvent is toluene, ODCB, or a combination thereof.

In step (b), the carbon starting material is dispersed in the organicsolvent, in a prescribed ratio. A prescribed ratio of a carbon startingmaterial to an organic solvent is defined as a ratio that will result indispersion of the carbon in the organic solvent, and in the formation ofthe cohesive assembly when the organic solvent is removed. For aparticular type of carbon starting material, there is a range ofprescribed ratios that are determined experimentally. Within that rangeof prescribed ratios, that type of carbon starting material willdisperse in the organic solvent and can form a cohesive assembly whenthe organic solvent is removed in a controlled manner.

If the ratios of the carbon starting material and organic solventamounts are outside the range of the prescribed ratios for thatparticular type of carbon starting material, a cohesive carbon assemblywill not form. For example, if the ratio of the carbon starting materialto organic solvent is too high, the carbon starting material may notdisperse completely in the organic solvent, but rather remain as powder,particles, flakes, or loose agglomerates, which may appear floating orsuspended in the organic solvent, or settle to the bottom of the organicsolvent in the container. If the ratio of carbon starting material toorganic solvent is too low, the carbon starting material may dispersecompletely. It may then form into an assembly during removal of theorganic solvent, but then break into pieces at the end of the process.Or, the dispersed carbon may assemble into particles or flakes, but notinto a monolithic cohesive assembly. Or, the dispersed carbon may simplyremain as a residue of powder, particles, flakes, or loose agglomeratesin the container when the organic solvent is removed.

In one embodiment, the prescribed ratio of the carbon starting materialto the organic solvent may be between about 0.015 and about 200 mg pergram of organic solvent, between about 0.01 and about 50 mg per gram oforganic solvent, between about 0.05 and about 50 mg per gram of organicsolvent, between about 0.1 and about 20 mg per gram of organic solvent,or between about 0.1 and about 10 mg per gram of organic solvent.“About”, as used herein, refers to +/−10% of the recited value.

In one embodiment, the carbon starting material comprising SWCNT isdispersed in the organic solvent comprising o-dichlorobenzene in aprescribed ratio of between about 0.1 and about 20 mg carbon startingmaterial per gram of o-dichlorobenzene.

In another embodiment, the carbon starting material comprising SWCNT isdispersed in the organic solvent comprising toluene, in a prescribedratio of between about 0.1 and about 20 mg carbon starting material pergram of toluene.

Dispersing, as used herein, is forming a stable suspension of carbon inthe organic solvent. A stable suspension is one in which no visiblepowder, particles, flakes, or loose agglomerates precipitate out of theorganic solvent or settle to the bottom of the mixture when nomechanical agitation is applied. In one embodiment, to disperse thecarbon in the organic solvent, the carbon is first combined with theorganic solvent in a container to form a mixture, and then the mixtureis mechanically agitated by one or more standard methods, for example,without limitation, mechanical stirring, and/or sonication, and/ormicrofluidization.

Dispersion of the carbon starting material in the organic solvent instep (b) may be carried out at a suitable temperature under a suitablepressure wherein the organic solvent is in a liquid form, i.e. themelting point and the boiling point of the organic solvent under thesuitable pressure. In one embodiment, the carbon starting material isdispersed in the organic solvent at a temperature between 0° C. and 100°C., between ambient room temperature and about 45° C. or between 10° C.and 30° C. Ambient room temperature (about 20° C.) and pressure aretypically suitable conditions.

Dispersion of the carbon starting material in the organic solvent may becarried out in the presence of one or more types of mechanicalagitation. The dispersion step may comprise more than one periods ofmechanical agitation. In each period, one or more types of mechanicalagitation may be carried out. The same type of mechanical agitationcarried out at different periods may have the same or differentparameters. In one embodiment, the dispersion step comprises threeperiods of mechanical agitation. For example, the first period ofmechanical agitation comprises mechanical mixing at 10,000 rpm for 30minutes in the presence of sonication, the second period of mechanicalagitation comprises mechanical mixing at 5,000 rpm for 10 minutes in thepresence of sonication, and the third period of mechanical agitationcomprises sonication for 2 hours at 45° C.

Mechanical agitation may be carried out at a suitable mixing speed (e.g.about 500 rpm to about 50,000 rpm) with a high shear mixer comprising arotor or impeller, together with a stationary component known as astator, or an array of rotors and stators. The mixer is used in a tankcontaining the carbon starting material and the organic solvent mixtureto be mixed or in a pipe through which the mixture passes, to createshear. In one embodiment, a two-stage mixing process starting at a firstspeed (e.g. about 10,000 rpm) for a first time period (e.g. about 30minutes) followed by a second speed (e.g. about 5,000 rpm) for a secondtime period (e.g. about 10 minutes) is adopted.

Sonication may be carried out by a variety of methods using commerciallyavailable equipment, examples include, without limitation, an ultrasonicprocessor with a probe or wand, and an ultrasonic bath or tank.Sonication may be carried out for a suitable time period at a suitableenergy level at a suitable temperature. In one embodiment, the suitabletime period is between about 0.1 and about 100 hours, between about 0.1and about 10 hours, or about 130 minutes. The suitable energy level isat least 0.01 watt/gram of solvent, or between 0.16 watt/gram of solventand about 1.6 watt/gram of solvent. The suitable temperature is the sameas described supra.

In one embodiment, the carbon starting material comprising SWCNT isdispersed in the organic solvent by mechanical stirring and/orsonication.

The dispersion of carbon starting material in the organic solvent instep (b) is different from commonly known methods of carbon dispersion,and in particular, CNT dispersion, in that no surfactant chemicals areneeded to disperse the carbon starting material. In one embodiment, thecarbon starting material is dispersed in the organic solventsubstantially free of surfactants. Surfactants are typically used todisperse carbon, and more specifically, carbon nanotubes, in a liquid,and in known methods of preparing carbon assemblies, surfactants areusually present as a residue. Examples of such surfactants include butare not limited to cetyl trimethylammonium bromide (CTAB),dodecylbenzenesulfonic acid sodium salt (NaDDBS), sodium cholate, sodiumdodecyl sulphate (SDS), polyoxyethylene (10) octylphenol (Triton X-100)and poly(ethylene oxide) (20) sorbitan mono-oleate (Tween 80).“Substantially free of surfactants,” as used herein, means less than10%, preferably less than 1%, and more preferably less than 0.1% (w/w)of surfactants is present relative to the weight of carbon startingmaterial used to prepare the assembly. Such surfactants are not neededto disperse the carbon in the organic solvent, when the carbon isdispersed in an organic solvent according to the method of theinvention.

Typically, ionic surfactants such as cetyl trimethylammonium bromide(CTAB), dodecylbenzenesulfonic acid sodium salt (NaDDBS), sodiumcholate, and sodium dodecyl sulphate (SDS), or nonionic surfactants suchas polyoxyethylene (10) octylphenol (Triton X-100, Dow Chemical Co.) andpoly(ethylene oxide) (20) sorbitan mono-oleate (Tween 80, ICI Americas,Inc.) are needed to effectively disperse CNTs in a liquid medium such asan aqueous-based solution or an organic solvent. These surfactants, whenused to disperse CNTs, may remain as a residue and thereby degrade theelectrical or mechanical properties of the final CNT-derived product.The cohesive assembly, when prepared by the present method, need notcontain surfactants. Therefore, the method of the current inventionrepresents a substantial improvement over existing techniques fordispersing CNTs in an organic solvent.

Furthermore, the carbon starting material is dispersed in the organicsolvent that is substantially free of a binding material (e.g. polymer,inorganic, or hybrid material). For industrial use, such bindingmaterials are typically required in order to form a carbon monolith. Forexample, to form a monolith of activated carbon for use in anelectrochemical double layer capacitor (EDLC), a polymer bindingmaterial such as PTFE (polytetrafluoroethylene) is needed to hold thecarbon particles together. Similarly, to form carbon aerogel monolithstypically requires impregnation with an organic-based aerogel that actsas a binder and is then later removed by pyrolysis. In the method of thecurrent invention, no such material is needed in order to form thecohesive carbon assembly as a monolith. “Substantially free of a bindingmaterial,” as used herein, means less than 10%, preferably less than 1%,and more preferably less than 0.1% (w/w) of binding material is presentrelative to the weight of carbon starting material used to prepare theassembly.

In certain embodiments, the carbon-organic solvent dispersion may beapplied to a surface after step (b). The surface may be that inside acontainer such as a dish, beaker, cylinder, tank, etc. In oneembodiment, the surface is a hydrophobic surface. Such hydrophobicsurface may be prepared in advance of applying the dispersion to thesurface, by applying any of various hydrophobic treatments or coatingsto the surface of a container or substrate material. For example,hydrophobic treatment solution described in U.S. Pat. No. 6,395,331B1 toYan et al, or other dimethyl containing, or fluorinated dimethylcontaining treatment solutions may be used to prepare a hydrophobicsurface. As another example, a container or substrate may be coated witha hydrophobic material such as Teflon®. The substrate or containermaterial onto which the hydrophobic treatment or coating may be appliedcan be a polymer, glass, metal, or ceramic.

In another embodiment, the surface comprises a hydrophilic surface (e.g.metal (e.g. aluminum, nickel, copper, gold, silver, platinum, and othermetals typically used as electrodes or current collectors), glass,silicon, plastic, and ceramic.)

To achieve a free-standing (self-delaminating) cohesive carbon assembly,the method further comprises applying the carbon-organic solventdispersion to a hydrophobic surface having water contact angle of atleast about 80°. To achieve an adherent cohesive carbon assembly as afilm, the method further comprises applying the carbon-organic solventdispersion to a hydrophilic surface having water contact angle of lessthan about 80°.

The dispersion may be applied to the surface by any known method, e.g.without limitation, spin-coating, dip-coating, flow-coating, spraycoating, casting, or a combination thereof. The spin-coating may becarried out at a spinning speed of about 10 rpm to about 10,000 rpm, orabout 300 rpm to about 5,000 rpm for a time of at least about 5 seconds.The dip-coating may be carried out at a withdrawing speed of about 0.01to about 1.0 cm/s, about 0.1 to about 0.4 cm/s, or about 0.2 cm/s.

In step (c), the organic solvent of the dispersion is substantiallyremoved, i.e. greater than 99% of the organic solvent is removed, in acontrolled manner, whereby the cohesive assembly of carbon is formed. Inorder for the cohesive assembly to form, the organic solvent must beremoved in a controlled manner. “Removing in a controlled manner,” asused herein, refers to removing the organic solvent in a rate and methodsuch that the dispersed carbon self-assembles into the cohesive assemblyof carbon, and the assembly remains intact as a single cohesive monoliththroughout the removal process, and after the organic solvent removal iscompleted. Any method to remove the organic solvent in a controlledmanner that allows the self-assembly of the carbon into a cohesiveassembly, and allows the assembly to remain as a cohesive assembly(monolith) after the organic solvent removal is completed, is within thescope of the invention. Examples of a controlled manner of removingorganic solvent may include slow evaporation, slow draining of theorganic solvent from the container, or a combination thereof. It isimportant not to remove the organic solvent so rapidly that will disturbor prevent the carbon from forming a cohesive assembly (monolith). It isalso important not to agitate the mixture during the removal process.

An example of a non-controlled manner of removing the organic solvent ispouring off the organic solvent by tipping the container (decanting), asthis would clearly disturb the formation of the cohesive assembly andnot result in a monolithic form. Another example of a non-controlledmanner is boiling of the organic solvent, as the accompanying vaporbubble generation and resultant agitation of the mixture would clearlydisturb the cohesive assembly and prevent the monolith from forming. Athird example of a non-controlled manner would be direct physicalremoval of the liquid at or through its exposed top surface in thecontainer, for example, by suctioning or siphoning through a tube orpipe. The breaking of the surface of the liquid by the tube or pipewould clearly interfere with the self-assembly of the carbon into amonolith.

In one embodiment, the controlled removal of organic solvent isconducted by slow evaporation. During the initial stages of thisevaporation, the dispersed carbon first nucleates on the top surface ofthe organic solvent, and then begins to assemble or coalesce into“islands” of carbon on the surface of the liquid. As evaporationprogresses, the islands grow and join together to form larger islands,eventually joining into a single monolithic disc, wafer, or film, i.e.,a cohesive assembly of carbon.

If the organic solvent is evaporated too quickly, a cohesive assembly ofcarbon will might not form. In such instances, the carbon may notnucleate on the top surface of the liquid, but may instead remain as apowder or particle residue in the container. Or, the carbon may nucleateon the surface, and islands may begin to form, but they will notcoalesce into a monolithic cohesive assembly, and remain asrandomly-shaped agglomerates of carbon rather than a cohesive assembly.Or, the islands may coalesce into a monolith, but then later break apartinto smaller pieces.

The specific conditions for controlled removal of organic solvent thatwill result in the formation of a cohesive assembly of carbon depend onthe type of the carbon starting material and the organic solvent, andcan be determined experimentally. For example, the organic solvent isremoved by evaporation at a suitable pressure, a suitable temperaturefor a suitable time. The suitable pressure may be between about 5,000Torr and about 0.001 Torr, between about 1,500 Torr and about 0.01 Torr,between about 800 Torr and about 0.01 Torr, between atmospheric pressure(about 760 Torr) and 0.01 Torr, between about 100 Torr and about 0.01Torr, between about 10 Torr and about 0.1 Torr, or between about 1 Torrand about 0.1 Torr. The suitable temperature may be between −20° C. andabout 200° C., between room temperature (about 20° C.) and about 180°C., or between about 40° C. and about 80° C. The suitable time may bebetween about 5 seconds and about 100 hours, between about 10 secondsand about 100 hours, between about 10 minutes and about 40 hours, orbetween about 1 hour and about 20 hours.

In one embodiment, the organic solvent is removed in a closed system ata pressure below atmospheric pressure. In another embodiment, theorganic solvent is removed by evaporation at atmospheric pressure.Either condition may be accompanied by heating to accelerate theevaporation of the organic solvent, provided that the rate ofevaporation is controlled such that formation of the cohesive assemblyof carbon is not disturbed or prevented.

The controlled removal of the organic solvent may also occur at atemperature and pressure without forming bubbles in the solvent, andwithout boiling of the solvent.

The evaporation of organic solvent may alternatively be controlled toform a cohesive assembly, by monitoring the evaporation rate of theorganic solvent and maintaining it within a range that will not preventor disturb the formation of the assembly. The lower end of the operablerange of evaporation rates is not particularly limited, except that avery low rate will result in an impractically long time to produce thecohesive assembly. The evaporation of organic solvent typically followsthe classic and well-known theory of two-stage drying of porous bodiesfirst proposed by Thomas .K. Sherwood in “The Drying of Solids—I”,Industrial Engineering and Chemistry 21, 1 (1929), 12-16, and in “TheDrying of Solids—II”, Industrial Engineering and Chemistry 21, 10(1929), 976-980. During the first drying stage, also known as theConstant Rate Period, the evaporation rate is preferably between about0.01 and about 10 milliliters/minute (ml/min), more preferably betweenabout 0.10 and about 1.0 ml/min. During the second drying stage, alsoknown as the Falling Rate Period, the evaporation rate is preferablybetween about 5×10⁻⁵ ml/min and about 5×10⁻² ml/min, more preferablybetween about 5×10⁻⁴ and about 7×10⁻³ ml/min.

Typically, greater than 99% of the organic solvent is removed byevaporation. Any remaining organic solvent may optionally be removedafter evaporation, by rinsing the cohesive assembly with an organicsolvent such as ethanol or isopropanol and then drying either at roomtemperature or with mild heating in an oven.

The formed cohesive carbon assembly may be removed from the containermanually or by lightly rinsing the inner surfaces of the vessel with afluid such as a dilute acid or organic solvent. The product assembly maythen receive a final drying at atmospheric pressure or under vacuum,which may be accompanied by mild heating.

In certain embodiments, a cohesive carbon assembly formed by the methodhas no residue of the organic solvent detectable by Fourier TransformInfrared Spectroscopy (FT-IR), Energy Dispersive X-Ray Spectroscopy(EDS), or Thermogravimetric Analysis (TGA).

In certain embodiments, the removed organic solvent may be collected.For example, a LN2 trap can be used to collect the removed organicsolvent. The recovered organic solvent may be reused in the methoddirectly or after purification if necessary.

Characterization of Cohesive Carbon Assemblies

A cohesive carbon assemblies prepared by the method of the invention arecharacterized by the substantial absence of surfactants during thepreparation and in the final product.

Cohesive carbon assemblies comprising CNTs, prepared by the method ofthe invention, feature high effective carbon packing density compared toother known CNT assemblies. The cohesive carbon assemblies typicallyhave effective CNT packing density of at least about 0.5 g/cm³, oftenhave densities higher than 1.0 g/cm³, and have shown densities as highas 1.5 g/cm³. For example, the cohesive carbon assemblies have effectiveCNT packing density of between about 0.3-1.9 g/cm³, preferably betweenabout 0.5-1.5 g/cm³, and more preferably between about 0.8-1.5 g/cm³ orbetween 1.0-1.5 g/cm³. This high density imparts these assemblies withgood mechanical strength and integrity. This high density alsocontributes to their superior electrical properties; in particular theirlow resistivity compared to other known CNT assemblies.

To determine the effective CNT packing density in a CNT-derived carbonassembly, first the apparent density of the assemblies is determined bycarefully measuring the weight of the assembly using a standardanalytical balance, then measuring the dimensions of the assembly usinga digital micrometer or optical or scanning electron microscope, thencalculating the volume of the sample from the dimensions, and dividingthe weight by the volume. This calculation provides the apparent densityof the assembly. Alternatively, the apparent density may be determinedusing a density balance and Archimedes' principle. Then, using one ofvarious methods such as energy dispersive x-ray spectroscopy (EDS),neutron activation analysis (NAA), or thermogravimetric analysis (TGA),the weight fraction of carbon (i.e., CNTs) in the assembly can bedetermined. Finally, the effective packing density of CNTs is calculatedby multiplying the apparent density by the weight fraction of carbon inthe assembly.

The assemblies can be produced in a desired size or shape, which isdetermined by the amount of carbon used to prepare the assembly, and bythe size and shape of the container in which the carbon assembly isprepared. This may allow the assemblies to be used in variousapplications requiring carbon assemblies of various shapes and sizes.When the organic solvent is removed from the dispersion, the carbonassembly typically self-assembles in the shape and size of the bottom ofthe vessel in the horizontal plane, with a vertical, i.e., perpendicularthickness that is determined by the amount of carbon used and the sizeof the container. Greater amounts of carbon will produce a thicker,wafer- or disc-like cohesive assembly, while less carbon will produce athinner, film-like assembly. Decreasing or increasing the diameter orcross-sectional area of the container used to prepare the assembly hassimilar effects on assembly thickness. In certain embodiments, theassembly has a thickness of about 0.02 μm to about 2,000 μm, or about0.1 μm to about 500 μm. In one embodiment, the assembly is aself-delaminating assembly having a thickness of about 0.1 μm to about2000 μm, about 1 μm to about 500 μm, or about 10 μm to about 50 μm. Inanother embodiment, the assembly is an adherent assembly having athickness of about 0.02 μm to about 2000 μm, about 0.02 μm to about 500μm, or about 0.02 μm to about 50 μm.

The cohesive carbon assemblies prepared by the method of the inventionalso feature low electrical resistivity compared to other carbonassemblies. These assemblies typically have resistivity of less thanabout 0.1 Ωcm, about 0.02-0.05 Ω-cm, and an electrical sheet resistanceof less than about 2,000 Ω per square, or between about 8 and about 17 Ωper square. This low electrical resistivity along with mechanicalstrength and integrity may allow various applications of theseassemblies, for example, as electrodes for batteries or supercapacitors,or as electromagnetic interference (EMI) shielding materials. This lowresistivity is related to the high effective carbon packing density ofthe assemblies in that as this density increases, empty space betweenindividual carbon entities such as nanotubes, tube bundles, or graphiteplatelets decreases, and the area of contact between these carbonentities increases. This naturally leads to more efficient and highercurrent flow through the assembly, thereby decreasing its resistivity.

Resistivity of the cohesive assembly is determined as follows: From eachassembly, a sample of rectangular or square geometry is cut thatpossesses lengths greater than 1 cm on all sides. The sample is mountedin a sample mount, and two electrical contact pairs (two currentcarrying and two voltage sensing) are directly compressed to the sample,in a standard Kelvin-type (4-point) probe configuration. The sample ispositioned such that the four metal tips of the four-point probe makedirect contact with the sample without puncturing through it.

A constant current is made to flow the length of the sample by using ahigh impedance current source. The current source is typically set toapply a current of 0.1×10⁻³ A, 1×10⁻³A, 10×10⁻³ A, or 100×10⁻³ A. Thevoltage drop across the sample is measured using a high impedancedigital voltmeter. The surface (sheet) resistance, R_(s) in Ω (or Ω/sq),of the sample is the ratio of the stable voltage registering on thevoltmeter, V, to the value of the output current of the current source,I, multiplied by the geometric factor π/1n2≈4.53:R _(s)=4.53 (V/I).

By measuring the thickness (t) of the sample, using a profilometer,digital micrometer, or scanning electron microscope, the electricalresistivity p of the sample in Ω-cm, can be calculated using theformula:ρ=R _(s)(t)

Additionally, cohesive carbon assemblies prepared by the method of theinvention using carbon starting material comprising CNTs (e.g. SWCNTs)display no more defects than the carbon starting material. A knowntechnique useful for evaluating the quality of CNTs, i.e., theconcentration of structural defects and amorphous carbon impuritiesincluded therein, is by measuring the intensity ratio of twocharacteristic Raman infrared spectral peaks, called the G/D ratio. TheG-line is a characteristic feature of the graphitic layers andcorresponds to the tangential vibration of the carbon atoms. The D-lineis a typical sign for defective graphitic structures. When determiningthe quality level of a CNT sample via Raman spectroscopy, the absoluteintensities of the G and D band peaks are not particularly relevant.Rather, the ratio of the intensity of the two peaks is the relevantmeasure. The comparison of the ratios of these two peaks' intensitiesgives a measure of the quality of the CNT samples. Generally, the G/Dratio is the ratio of good to bad CNT peaks. Thus, CNTs having a higherG/D indicate a lower amount of defects and a higher level of quality.

A G/D ratio is typically determined using a Raman spectroscopytechnique. Any of various commercially available instruments may be usedto measure the G and D band intensities and to calculate the G/D ratio.One example of such an equipment is available from HORIBA Jobin YvonInc., Edison, N.J., under the model name LabRAM ARAMIS.

In a CNT sample, the G/D ratio may change after treatment. The presentmethod has the advantage that the G/D ratio of the formed cohesivecarbon assembly is about the same or greater than the G/D ratio of thecarbon starting material, indicating that the method does not introducestructural defects during the process.

The method of the current invention provides additional distinctadvantages over existing methods for fabricating a carbon assembly, andin particular, for fabricating such an assembly as an adherent wafer orfilm onto a metallic substrate or backing sheet made of, for example,aluminum, copper, iron, nickel, platinum, gold, silver, titanium, alloysthereof, and so on.

Firstly, the current method, compared to other known methods utilizinghalogens as the dispersing solvent, enables the use of metalliccontainers or surfaces onto which the dispersed carbon may be cast ordeposited. It is well-known that halogens such as bromine are highlycorrosive to many metals, including those commonly used in electroniccomponents such as aluminum, copper, nickel, iron, and so on. Aluminumin particular is a commonly used material for current collectors incapacitors, batteries, and other energy storage devices. Bromine reactsviolently on contact with aluminum, producing AlBr₃. Therefore, it isnot suitable to utilize bromine as a dispersing solvent for carbonnanotubes or other forms of carbon to produce a cohesive assembly in ametal container, or deposit a cohesive carbon film on a metal substrate.The current method, employing a selected organic solvent that isnon-corrosive to metals as a dispersing medium, enables the fabricationof a cohesive assembly of carbon in a metal vessel, or as a cohesivefilm on a metal substrate.

Second, the current method enables preparation of an adherent, cohesivecarbon assembly on a metal substrate without the use of any bondingmaterial to attach the carbon assembly to said substrate. Standardindustrial methods for attaching carbon-based electrodes to metalbacking sheets, for example, in the assembly of electrochemicaldouble-layer capacitors (EDLCs), typically entails the use of a bondingmaterial. These materials may have conductive additives to reduce theirelectrical resistance, but they are typically polymer-based and areinherently less conductive than both the carbon assembly and the metalbacking sheet. Thereby, the process of attaching the carbon assembly tothe metal with a bonding material results in increased contactresistance between the carbon and metal, and reduced performance of thedevice overall. The current method, in contrast, allows the fabricationof an adherent carbon assembly on a metal substrate, resulting in anarticle comprising a carbon assembly attached to a metal substrate, withno bonding material, having reduced contact resistance between thecarbon and the metal. This results in improved performance of the devicein which this article is used, such as an EDLC, fuel cell, battery, etc.

Applications of Cohesive Carbon Assemblies

Another aspect of the invention relates to an article comprising asubstrate and a cohesive carbon assembly coated onto at least onesurface of the substrate, wherein the cohesive carbon assembly has beenprepared by the method described supra.

The cohesive carbon assembly may be otherwise treated after itsfabrication, in order to enhance its performance for certainapplications. For example, for application as a fuel cell electrode, acoating of metal particles, such as platinum, may be advantageous forits catalytic properties. For battery electrode applications, metalparticle coatings such as iron, platinum, palladium, nickel, lithium, orother appropriate metals may be desired. Such particle coatings may beaccomplished using a method disclosed by Grigorian et al in US PatentApplication Publication US 2009/0015984A1, which is hereby incorporatedby reference.

The cohesive carbon assembly of the present invention has particularadvantages over other types of carbon assemblies for use as an electrodeor current collector in electrochemical capacitors, fuel cells, orbatteries. These advantages include its inherent mechanical strength andintegrity, low electrical resistivity, ability to be fabricated and/orfurther modified to a desired shape and size, and high carbon packingdensity that results in excellent energy storage capabilities (i.e.,power density and energy density).

The cohesive carbon assembly is appropriate for use as an electrode in acapacitor or a capacitor cell, which are used interchangeably in thisapplication, due to its desirable combination of electrical andmechanical properties. The capacitor may be of any type that comprisestwo electrodes separated by an insulating material. The capacitor may bea simple electrostatic capacitor with a bulk dielectric materialseparating the two conducting electrodes, or an electrolytic capacitor,in which one or both of the electrodes comprises an electrolyte. Thecohesive carbon assembly is especially suitable for use as an electrodein an electrochemical double-layer capacitor (EDLC), sometimes referredto as a “supercapacitor” or “ultracapacitor”.

The cohesive carbon assembly, and in particular the assembly comprisingcarbon nanotubes, may be altered after fabrication by the inventedmethod into an electrode of suitable size or shape for directinstallation into a capacitor cell. The electrode may be disc-shaped,i.e. round or ovoid, or it may be a polygon having three or more sides.The size and shape are determined only by the size and shape of thecapacitor device in which it will be used. The thickness of theelectrode is not particularly limited, but certain thicknesses may bepreferable for use in capacitor devices. If the electrode is too thick,resistance of the electrode may be too high or energy transfer will beinefficient. If it is too thin, it will not have the necessarymechanical integrity or energy storage potential for capacitor use.Generally, the thickness is preferably between about 0.02 μm and about2,000 μm, or between about 0.1 μm and about 500 μm. In one embodiment,the assembly is a self-delaminating assembly having a thickness of about0.1 μm to about 2000 μm, about 1 μm to about 500 μm, or about 10 μm toabout 50 μm. In another embodiment, the assembly is an adherent assemblyhaving a thickness of about 0.02 μm to about 2000 μm, about 0.02 μm toabout 500 μm, or about 0.02 μm to about 50 μm.

The cohesive carbon assembly may be optionally purified of metallicimpurities prior to use as a capacitor electrode. Specifically, for anassembly comprising carbon nanotubes, removal of metallic impuritiesthat are residues of the CNT synthesis process may improve theelectrical and energy storage properties of the assembly. Thispurification may be accomplished by various means, with treatment with ahalogen gas, and chlorine gas in particular, being the preferablemethod. The parameters of this treatment process are not particularlylimited, provided the carbon is not damaged or degraded during theprocess.

In one embodiment, the removal of metallic impurities from the cohesivecarbon assembly is achieved by treatment with chlorine gas at elevatedtemperature in a controlled-atmosphere furnace such as a quartz-tubefurnace. The chlorine gas is typically used in the form of a mixturewith an inert carrier gas such as nitrogen, helium, or argon. Thechlorine content in the mixture is typically between 1 and 20% (v/v),preferably between 2 and 10%, more preferably about 5%. The temperaturein the furnace during the treatment is typically between 800° C. and1200° C., preferably between 900° C. and 1100° C. The time needed forthe treatment depends on various factors such as the amount of materialto be treated, the type of gas used, furnace design and method of gasdelivery, etc. Typically, however, the time of treatment is betweenabout 15 and 180 minutes, preferably between 30 and 90 minutes. The flowrate of the gas mixture also depends on various factors including thosementioned, but in the example embodiment of a quartz-tube furnace, thelinear flow rate of the gas is typically between 0.1 and 20 cm/min,preferably between 0.25 and 10 cm/min.

To evaluate the performance of a cohesive carbon assembly as a capacitorelectrode, one electrode may comprise a cohesive carbon assembly in anasymmetrical capacitor cell, or two electrodes may each comprise acohesive carbon assembly in a symmetric capacitor cell. The method ofevaluating the performance of the cohesive carbon assembly as acapacitor electrode is not particularly limited, and there are variousstandard methods known in the field. Typically, the capacitor cellcomprising the two electrodes separated by an insulating material isassembled with metal plates as current collectors attached to the outersurfaces of the electrodes. The cell is then submerged in an appropriateelectrolyte and a voltage is applied. For EDLCs, the preferable appliedvoltage (absolute value) is between 0 and 2 volts, or between 0 and 4volts, to evaluate performance for consumer electronics and vehicleapplications. Analytical methods used to evaluate the electrodeperformance may include leakage current measurement, electrochemicalimpedance spectroscopy (also known as dielectric spectroscopy),charge/discharge cycling using commercially available test equipment,and the like.

To determine the performance advantage of the cohesive carbon assemblyas a capacitor electrode, the properties measured are compared to thoseof capacitors comprising electrodes of other standard materials such asactivated carbon, or other types of CNT-based electrodes such as CNTforest-derived materials. Cohesive assemblies of carbon prepared by thepresent method in general show superior power performance as capacitorelectrodes, compared to activated carbon electrodes and other types ofCNT-based electrodes. The superior performance includes lower leakagecurrent and faster discharge time, and a better combination of powerdensity and energy density, important parameters for electric vehicleand consumer electronics applications. Furthermore, the cohesiveassemblies possess the necessary mechanical integrity to be packageddirectly into sealed capacitor cells, whereas the other CNT-basedelectrodes do not.

Similarly as for a capacitor, the cohesive carbon assembly of thepresent invention is suitable for use as an electrode in a battery. Thebattery may be of any type comprising two electrodes separated byelectrolyte. Of particular interest is the Li-ion battery type, in whichthe cohesive carbon assembly is suitable for use as the anode or cathodematerial, or both. As for the capacitor application, the size, shape,and thickness of the battery electrode comprising the cohesive carbonassembly are not particularly limited. Preferred thicknesses are alsosimilar to those for capacitor electrodes.

The cohesive carbon assembly may be used as a battery electrode in itsas-prepared form, i.e. as an assembly comprising nearly pure carbon. Or,the assembly may be further treated after it is fabricated by, forexample, coating with metal particles using the method described in US

Patent Application Publication US 2009/0015984A1. The metal coating maybe selected such that the assembly is suitable for use as the anode, orit may be selected such that the assembly is suitable for use as thecathode. The appropriate metal coating depends on the overall design ofthe cell.

In its as-prepared form, a cohesive carbon assembly of carbon nanotubes,and more preferably, a cohesive assembly of SWCNT, is especiallyappropriate for use as the anode in a Li-ion battery cell, with acorresponding cathode comprising one or more Li-containing oxides suchas LiCoO₂, LiFePO₄, or LiNiCoAlO₂. The electrode comprising the cohesivecarbon assembly requires no binder material and can be installed in abattery cell in its as-prepared form.

A battery containing a cohesive carbon assembly electrode may beperformance tested using a standard method such as is described by Y.NuLi et al in “Synthesis and characterization of Sb/CNT and Bi/CNTcomposites as anode materials for lithium-ion batteries,” MaterialsLetters 62 (2008) 2092-2095, or by J. Yan et al in “Preparation andelectrochemical properties of composites of carbon nanotubes loaded withAg and TiO₂ nanoparticle for use as anode material in lithium-ionbatteries,” Electrochimica Acta 53 (2008) 6351-6355In this manner, theperformance of a cohesive carbon assembly-based lithium-ion batteryanode is thereby compared to the performance of lithium-ion batteryanodes composed of other materials such as graphite, hard carbon (i.e.diamond-like carbon), titanate, silicon, germanium, other CNT-basedelectrodes that require binder or structural support, and the like.

The cohesive carbon assembly of the present invention is also suitablefor use as an electrode in a fuel cell. In a PEM-type fuel cell, theelectrode comprises a catalyst support layer and a gas diffusion layer(GDL). The cohesive carbon assembly, as described earlier, has lowresistivity and high mechanical strength and integrity. Furthermore, itexhibits sufficiently high pore volume to allow the needed diffusion ofgaseous species (hydrogen, oxygen, water vapor) for fuel cell use. Thetotal pore volume of the assembly comprising SWCNT is typically greaterthan 1.0 cm³/g, often greater than 1.5 cm³/g, and has been observed toexceed 2.0 cm³/g. Total pore volume correlates with total porosity, andapproximately correlates with gas permeability. Therefore, the cohesivecarbon assembly, and in particular the SWCNT assembly, is appropriatefor use as either the catalyst support or the GDL, or as bothsimultaneously.

The size and thickness of the cohesive carbon assembly, for use in afuel cell, are not particularly limited. However, the thickness shouldbe selected such that the desired level of gas permeability ismaintained, and, when used as the catalyst layer, such that the desiredlevel of catalytic activity through the layer is achieved. The thicknessof the cohesive carbon assembly of this invention when used as acatalyst layer in a fuel cell is typically 5-20 μm thick. The thicknessof the cohesive carbon assembly of this invention when used as a GDL ina fuel cell is typically 100-300 μm thick.

For use as a catalyst support in a fuel cell, the cohesive carbonassembly is typically coated with metal particles that act as thecatalysts for the electrochemical reaction. The type of metal particlesis chosen based on whether the electrode is to be the cathode or anodein the fuel cell. For example, if the assembly is to be the anode, themetal may be platinum. If the assembly is to be the cathode, the metalmay be nickel. The coating may be accomplished by any appropriatemethod, for example, by the method described in US Patent ApplicationPublication US 2009/0015984A1. This coating method comprises twoessential steps: (1) the assembly is treated with a halogenatedprecursor, such as platinum iodide (PtI₂), nickel iodide

(NiI₂), palladium iodide (PdI₂), or the like, to form a halogenatedintermediate; (2) residual halogen is removed and the metallic speciesdeposited on the assembly are reduced to pure metal by heating combinedwith hydrogen gas treatment.

To evaluate the performance of the cohesive carbon assembly as acatalyst support, GDL, or both, a PEM-type fuel cell is assembled withthe cohesive carbon assembly component in place of the standard materialtypically used for that component. For example, if the cohesive carbonassembly is the catalyst support, then it is coated with the catalystmetal particles and then installed in the fuel cell in place of thestandard catalyst support, usually Pt-coated or Ni-coated carbon black.If the cohesive carbon assembly is the GDL, then it is installed in thefuel cell in place of the standard GDL, usually carbon paper or carboncloth. If the cohesive carbon assembly is both the catalyst support andthe GDL, it is installed in place of both standard components. The fuelcell with the cohesive carbon assembly installed may be performancetested by any standard method, such as that described by B. Fang et alin “Nanostructured PtVFe catalysts: Electrocatalytic performance inproton exchange membrane fuel cells,” Electrochemistry Communications 11(2009) 1139-1141. Performance parameters such as cell voltage and powerdensity vs. current density are thus compared with those of standardfuel cells or fuel cells containing other potential alternative catalystsupport/GDL materials.

Energy storage devices such as capacitors, batteries, and fuel cells,typically comprise a current collector and an electrode on one side ofan insulating material or an electrolyte, and another current collectorand another electrode on the other side of the insulating material orelectrolyte. For example, in an electrostatic capacitor, the separatingmaterial is an insulating material, whereas in EDLCs, batteries, andfuel cells, the separating material is an electrolyte. The electrolytein EDLC, battery, or fuel cell is divided by a thin membrane allowingionic conduction between the electrodes. The cohesive carbon assembly ofthe present invention is appropriate for use as a current collector inthese energy storage devices, due to its low resistivity, goodmechanical properties, and ability to be fabricated into a desired shapeand size.

The cohesive carbon assembly may further be used concurrently as afree-standing electrode and a current collector. A free-standingelectrode, as used herein, refers to an electrode containing thecohesive carbon assembly as the only conductive material. The advantageof this is that the entire mass contributes to the usable electrodecapacity. This is in contrast to a conventional electrode where theusable electrode capacity is decreased because of mass averaging of theactive material composite layer and a metal current collector.Typically, the current collector is an aluminum or copper plate, withnotably higher mass density (2.7 and 8.8 g/cm³, respectively, for Al andCu) than that of the CNT electrode (˜0.7 g/cm³), which in turn addssignificant weight to the device.

Another advantage for free-standing electrodes is the ability to adjustthe electrode thickness that might lead to performance improvement. Forexample, in electrochemical double-layer capacitors (EDLC), thinnerelectrodes having lower resistance provide higher power density. Thisapproach to performance improvement is not feasible with conventionaldesigns due to the relative increase in the mass percent of the currentcollector.

Other advantages, more specific to the design of particular energystorage devices, are foreseeable. For example, in a battery, eliminationof the copper substrate would allow for cycling below 2.5 V (the typicalpotential where oxidation of the copper substrate initiates), thusincreasing the depth of discharge and creating the opportunity tomaintain a near-zero volt state-of-charge for prolonged storage. Ingeneral, substitution of metal current collectors with the cohesivecarbon assembly of the present invention enables entirely new designsfor these devices.

The invention is illustrated further by the following examples that arenot to be construed as limiting the invention in scope to the specificprocedures or products described therein.

EXAMPLES Example 1 Dispersion of SWCNT in ODCB

A stable dispersion of SWCNT in o-dichlorobenzene (ODCB) was produced asfollows:

-   (1) 600 mg of SWCNT (Thomas Swan “Elicarb SW”) were combined with    500 grams of ODCB to provide a first mixture.-   (2) The first mixture was mixed and dispersed using a high shear    mixer (10,000 rpm) and optional simultaneous sonication in an    ultrasonic bath for 30 min in a sealed container to provide a second    mixture.-   (3) The mixer speed was then reduced to 5,000 rpm, so that the    solution was not splashed on the wall of the container. 100 grams of    ODCB were added by spraying the wall of the container with a wash    bottle, so that no SWCNT remained stuck to the wall of the    container. The obtained mixture was mixed at 5000 rpm and optionally    in the presence of simultaneous sonication in ultrasonic bath for 10    min to provide a third mixture.-   (4) The third mixture in a sealed bottle was sonicated in an    ultrasonic bath for 2 hrs at 45° C. after removing the high shear    mixer probe, to provide a fourth mixture.-   (5) The fourth mixture was a SWCNT-ODCB dispersion ready to be used    for coating or casting.

Alternatively, when no sonication was carried out during the mechanicalmixing, the third mixture was sonicated in an ultrasonic bath for 1hour, or 4 hrs at 45° C. to provide a SWCNT-ODCB dispersion.

Example 2 Self Delaminating and Self Standing Cohesive Assembly of SWCNT

Ultrasonically cleaned Petri dishes 9 cm in diameter were used as themolds for casting. The Petri dishes were coated with a hydrophobiccoating solution such as is described in U.S. Pat. No. 6,395,331B1 toYan et al. The hydrophobic coating resulted in a surface having watercontact angle ≧80°. Hydrophobic coating on molds was prepared bydip-coating, flow-coating, spin-coating, or spray coating, and thencuring (and drying) at 200° C. for 1 hour.

The SWCNT-ODCB dispersion prepared in Example 1 was slowly cast into thehydrophobic coated molds under ambient conditions. Each mold was castwith a different amount of SWCNT-ODCB dispersion so that the dishescontained between 5 mg and 2 grams of SWCNT.

If any dispersed SWCNT adhered to the wall of the mold after casting,about 5 grams of ODCB were sprayed to wash the SWCNT down into the castSWCNT-ODCB dispersion.

The cast molds were placed in a vacuum oven at room temperature. Vacuumwas slowly applied in the oven for 10 minutes so that no bubbles orboiling of the solvent in the mold occurred. A liquid nitrogen vaportrap was placed between the vacuum oven and the pump. Evaporated solventwas collected in the trap. Optionally the molds were covered with SaranWrap films with pin-holes to control solvent evaporation.

The oven temperature was raised to 30° C. to accelerate the solventevaporation speed. The solvent was substantially removed from the moldafter about 10 hours. The molds were removed from the vacuum oven andheated at 200° C. for 3 hr in a conventional oven, then cooled toambient temperature.

After substantially removing the solvent by evaporation, free-standing,SWCNT assemblies (wafers) were formed that could be easily lifted out ofthe molds.

The weight and thickness of the resulting cohesive SWCNT wafers dependedon the amount of dispersion initially cast into the mold. For example,three intact SWCNT wafers obtained by the above procedure had weights of72 mg, 95 mg, and 123 mg with 64 cm² surface area for each (9 cmdiameter). Their respective thicknesses were about 16, 21, and 27 μm.

Example 3 Adherent, Cohesive SWCNT Assemblies on Substrates (Cast)

About 165 mg of the SWCNT-ODCB dispersion prepared according to Example1 was cast into a Petri dish lined with aluminum foil. The ODCB solventwas removed by evaporation as described in Example 2. An adherent,cohesive SWCNT assembly as a coated film, about 20 μm thick, was formedon the aluminum foil surface. No delamination or loss of adherence wasobserved after the SWCNT-aluminum article was heated at 300° C. for 4hrs.

About 165 mg of the SWCNT-ODCB dispersion prepared according to Example1 was also cast into a cleaned glass Petri dish (untreated withhydrophobic coating). The ODCB solvent was removed by evaporation asdescribed in Example 2. An adherent, cohesive SWCNT assembly was formedas a coated film on the glass surface (FIG. 2). No delamination or lossof adherence was observed after the coated glass was heated at 400° C.for 3 hrs, nor when the coated glass was rinsed with a solvent such asacetone, ODCB, or IPA.

The SWCNT assembly in the glass dish was separated from the glasssurface by immersing in 20% HF solution for at least 1 minute. It wasthen rinsed with water and dried in air, resulting in a free-standingcohesive SWCNT assembly.

Example 4 Cohesive SWCNT Assembly on a Substrate (Spin-Coated)

One (1) milliliter of the SWCNT-ODCB dispersion prepared according toExample 1 is spin-coated on a silicon wafer substrate at 500 rpm for 30sec. The ODCB solvent is removed by evaporating in air for at least 1minute. A cohesive SWCNT assembly as a coated film is formed on thesubstrate, having a thickness of about 0.5 μm.

Example 5 Cohesive SWCNT Assembly on a Substrate (Dip-Coated)

The SWCNT-ODCB dispersion prepared according to Example 1 is placed intoa rectangular tank at least 6 inches wide, 1 inch deep, and 5 incheshigh. Sufficient amount of the dispersion is placed into the tank tofill it to within 1 inch of the top. A 4×6 inch sheet of copper,aluminum, or other metallic substrate, or a silicon wafer, is loweredinto the tank of

SWCNT-ODCB dispersion. The substrate is then withdrawn vertically fromthe tank at a speed of 0.2 cm/s. The ODCB solvent is removed byevaporating in air for at least 1 minute. A cohesive SWCNT assembly as acoated film is formed on the substrate, having a thickness of about 5μm.

Example 6 Cohesive SWCNT Assembly on a Substrate (Spray-Coated)

The SWCNT-ODCB dispersion prepared according to Example 1 is sprayed onan aluminum foil substrate. The ODCB solvent is removed by evaporationin a vacuum oven at 0.25 Torr and 50° C. for at least 10 minutes. Acohesive CNT assembly as a coated film is formed on the substrate,having a thickness of about 50 μm.

Example 7 Characterization of Cohesive Carbon Assembly

(I) Electrical Sheet Resistance and Resistivity

To be useful as a current collector for such devices as a capacitor,fuel cell, or battery, a material needs to have sufficiently lowresistivity (on the order of 10⁻² Ω-cm or below) and sufficientmechanical robustness (high tensile strength and resistance tobreakage).

To establish that the cohesive assemblies have sufficiently lowresistivity to be used as current collectors, assemblies preparedaccording to Examples 2 and 3 were measured for electrical sheetresistance and resistivity as follows:

From each assembly, a sample of rectangular or square geometry was cutwith lengths greater than 1 cm on all sides. Each sample was mounted ina sample mount, and two electrical contact pairs (two current carryingand two voltage sensing) were directly compressed to the sample, in astandard Kelvin-type (4-point) probe configuration. The sample waspositioned such that the four metal tips of the four-point probe madedirect contact with the sample without puncturing through it.

A constant current of 1 mA was made to flow the length of the sample byusing a high impedance current source. The voltage drop across thesample was measured using a high impedance digital voltmeter. Thesurface (sheet) resistance, R_(s) in Ω (or Ω/sq), of the sample wasdetermined from the ratio of the stable voltage registering on thevoltmeter, V, to the value of the output current of the current source,I, multiplied by the geometric factor π/1n2≈4.53:R _(s)=4.53 (V/I).

The thickness (t) of each sample was measured using a profilometer,digital micrometer, or scanning electron microscope, and the electricalresistivity ρ of each sample in Ω-cm, was then calculated using theformula:ρ=R _(s)(t)

Sheet resistances of SWCNT assemblies prepared according to Examples 2and 3 were between 8 and 17 Ω per square.

Resistivities of cohesive carbon assemblies prepared according toExamples 2 and 3 were between about 0.02 and 0.05 Ω-cm.

Resistivities of the SWCNT assemblies were sufficiently low such thatthey could be utilized as current collectors in electronic storagedevices such as capacitors, fuel cells, or batteries. Moreover, cohesiveassemblies fabricated with the present invention possess the necessarymechanical properties to be used as current collectors, replacingcurrent collectors made from metals such as aluminum or copper. This isin direct contrast to other types of carbon assemblies, including, forexample, activated carbon, and other CNT-based assemblies such as thosemade from CNT forests, which do not possess the necessary robustness tobe used as current collectors in place of metal plates.

(II) Raman Spectrum

SWCNT assembly prepared according to Examples 2 and the correspondingcarbon starting material were characterized by Raman spectrum using astandard method. The SWCNT wafer showed improved Raman G/D ratio of 4.9on the top surface and 7.1 on the bottom side of the wafer compared tothat of the carbon starting material (as received CNT powder, Raman G/Dratio 4.6) (FIG. 3). This suggests that the ratio of carbon nanotubes toother forms of carbon such as amorphous carbon was somewhat higher,and/or that the concentration of defects in carbon nanotubes wassomewhat lower, towards the bottom of the assembly.

(III) Scanning Electron Microscopy (SEM) Imaging

SWCNT assemblies prepared according to Examples 2 and 3 were imaged andcharacterized by SEM (JSM-7500F, JEOL Ltd., Tokyo). The images showedthat the SWCNT assemblies obtained formed a structure of inter-wovennanotubes during the solvent evaporation process and preserved thenanotube aspect ratio of length to diameter.

Example 8 Capacitor Electrode Comprising a Cohesive Assembly of SWCNT

Cohesive carbon assemblies were prepared following the proceduredescribed in Example 2. The SWCNT assemblies were about 9 cm in diameterand about 20-35 μm thick (measured using a profilometer, model Dektak150, Veeco Instruments Inc., Plainview, N.Y.). Discs about 0.625 inch indiameter were cut from the assemblies using a standard laboratory blade.

Some of the discs were placed in a sealed quartz tube inside a furnaceat room temperature (about 20° C.). The tube was purged for one hour byflowing helium through it at 20 sccm. The discs were then heated in thefurnace at 10° C./minute to 1000° C. while continuing the flow ofhelium. While holding the temperature at 1000° C., helium flow wasstopped, and a mixture of 5% chlorine and 95% argon gas was introducedat 20 sccm. These conditions were maintained for 1 hour, then the gaswas switched back to helium at 20 sccm for 30 minutes. The gas was thenchanged to a mixture of 5% hydrogen and 95% argon at 20 sccm for 30minutes to remove residual chlorine. Then, the gas was switched back to20 sccm helium and maintained for 2 hours. The furnace was then coolednaturally to room temperature.

The discs treated with chlorine as above, and some non-treated discs,were then dried under vacuum at 195° C. for 12 hours immediately priorto further use.

For comparison with the SWCNT discs, Activated Carbon (AC) with theproduct name Norit DLC Super 30 was obtained from Norit Nederland BV(Amersfoort, The Netherlands). A disc-shaped piece about 0.625 inch indiameter and between 40 and 60 μm thick was formed from the AC powderusing standard manufacturing methods. The AC disc was dried at 60° C.for 1 hour immediately prior to further use.

Electrochemical double-layer capacitor (EDLC) cells were fabricatedusing the SWCNT and AC discs. Prototype cells were assembled in a drybox using metal plates clamped against each electrode face as currentcollectors. The cells were tested for their properties and performanceas electrodes in symmetric electrochemical capacitors rated at 2.0volts, using 1.0M tetraethylammonium tetrafluoroborate (TEATFB) salt inpropylene carbonate as the electrolyte.

Test capacitor cells were conditioned by holding them at 2.0 V for tenminutes, then charge/discharge cycled using a battery/capacitor tester(Model BT2000, Arbin Instruments, College Station, Tex.) thirty timesbetween 1.0 and 2.0 V using 2.5 mA current. Then, electrical performancemeasurements were made in the following order:

-   -   1. Leakage current after 30 minutes at 1.0, 1.5, and 2.0 V    -   2. EIS (electrochemical impedance spectroscopy) measurements at        2.0 V bias voltage    -   3. Constant-current and constant-power charge/discharge        measurements using the Arbin tester

Representative results of the above measurements are summarized in Table1.

Equivalent series resistances (ESR) of all cells were comparable.

The 30 minute leakage current of cells fabricated with electrodes madefrom both non-treated and Cl₂-treated SWCNT assemblies was superior(i.e. lower) compared to that of the cell fabricated with AC electrodes.Chlorine-treated SWCNT cells showed slightly better leakage currentcompared to non-C1₂-treated cells, but the difference might bestatistically insignificant. The much lower leakage current of the SWCNTcells suggests that they may be operated at substantially highervoltages compared to AC-based cells.

The SWCNT cells exhibited very high discharge rate, with fullcapacitance discharge times on the order of about 0.3-0.4 seconds, orless, which was retained up to 5 A/g current, compared to about 2-3seconds for the AC cell. Furthermore, the AC cell did not retain fullcapacitance to this same current level. This indicates that the SWCNTcells showed superior power performance compared to the AC cell.

Power density of the SWCNT cells was estimated to be at least 100 kW/kg.This is superior to the power density of typical commercial AC-basedEDLCs, which is about 10 kW/kg or less, and is at least equivalent tothe power performance of any currently available commercial EDLC.

TABLE 1 Performance of Capacitor Cells Utilizing SWCNT Electrodes of thePresent Invention, Compared to Activated Carbon Electrode. EIS FrequencyCell ID 30 minute leakage Discharge Power for 45° and ESR current (μA)Time Density phase Type (Ω) 1.0 V 1.5 V 2.0 V (sec) (kW/kg) angle (Hz) 1(No Cl₂) 0.64 1.6 2.3 5.1  0.3-0.4* >100^(#) 2.7 2 (No Cl₂) 0.63 1.5 2.44.9 2.2 3 (Cl₂ 0.50 0.8 1.6 4.0 2.9 treated) 4 (Cl₂ 0.51 0.7 1.2 3.8 2.3treated) 5 (Cl₂ 0.72 0.6 1.3 3.5 2.0 treated) AC 0.54 3.9 7.3 33.1 ~2-3 ~10  0.4-0.5 *Minimum measurable full capacitance discharge time underthe test conditions; actual time is lower. ^(#)Maximum measurable powerdensity under the test conditions; actual power density is higher.

Due to limitations within the test, absolute full capacitance dischargetime and power density of the SWCNT cells could not be determined. Forthese two parameters, the SWCNT cells showed power performance in excessof the measurement capability of the test equipment.

Another strong indicator of pulse power performance of a capacitordevice is the frequency at which the complex impedance phase anglereaches 45°. A higher frequency indicates better performance. Capacitorsfabricated from SWCNT electrodes showed 45° phase angle frequency of2.0-2.9 Hz, whereas the capacitor based on AC showed 45° phase anglefrequency of 0.5 Hz. For this performance metric, C1₂-treated andnon-treated SWCNT cells performed similarly.

Overall, SWCNT electrodes of the present invention out-performedcommercial activated carbon currently used as the standard electrodematerial in EDLC devices, in terms of pulse power performance.

Example 9 Battery Electrode Comprising a Cohesive Assembly of SWCNT

A cohesive carbon assembly is prepared following the procedure describedin Example 2. The SWCNT assembly is about 9 cm in diameter and about 40to 60 μm thick.

A section of appropriate size and shape is cut from the assembly andtested for its performance as an anode in a lithium-ion battery, usingthe method described by Y. NuLi in Materials Letters 62 (2008)2092-2095.

The test method consists of the following essential steps: (1) thecohesive SWCNT assembly is installed in a test battery cell, (2) thecell is discharged, and (3) the power and energy densities from thedischarge curves are measured.

Then, the data for the cell with the SWCNT anode is compared with thesame data obtained from a sampling of similar cells having other typesof anode materials. The performance of the SWCNT assembly-basedlithium-ion battery anode is thereby compared to the performance oflithium-ion battery anodes composed of other materials such as graphite,hard carbon (i.e. diamond-like carbon), titanate, silicon, germanium,other CNT-based electrodes that require binder or structural support,and the like.

Example 10 Fuel Cell Electrode Comprising a Cohesive Assembly of SWCNT

A cohesive carbon assembly is prepared following the procedure describedin Example 2. The SWCNT assembly is about 9 cm in diameter and about 40to 60 μm thick (measured by profilometer).

A piece of the SWCNT assembly is analyzed by nitrogenadsorption/desorption using a model TriStar 3000 equipment manufacturedby Micromeritics Instrument Corp., Norcross, Ga. The assembly has a BETsurface area of 1680 m²/g, and a total desorption pore volume of 1.75cm³/g. The density of the assembly is determined to be about 0.5 g/cm³by dimensional and weight measurements. The porosity of the assembly isthereby calculated as about 88%.

A section of appropriate size and shape is cut from the assembly and thesection is then coated with platinum metal particles according to amethod described in US Patent Application Publication US 2009/0015984A1.

The Pt-coated section of SWCNT assembly is evaluated for its performanceas a fuel cell electrode, using the method described by B. Fang et al,Electrochemistry Communications 11 (2009) 1139-1141. The cell voltageand power density vs. current density behavior of the fuel cellcontaining the SWCNT assembly-based electrode, is then compared to theperformance of standard fuel cells containing carbon black, carbonpaper, and/or carbon cloth-based electrodes, and to the performance offuel cells containing other potential alternative electrode materials.

Example 11 Self Standing Cohesive Assembly of SWCNT from TolueneDispersion

A dispersion of SWCNT in a liquid solvent was prepared in a similar wayas described in Example 1 (steps 1 through 4), except toluene was usedas the dispersing solvent in place of ODCB, and 250 mg of SWCNT weredispersed in 217.5 g (about 250 ml) of toluene. The resulting mixturewas a stable SWCNT-toluene dispersion ready to be used for coating orcasting.

About 43.5 g (50 ml) each of the SWCNT-toluene dispersion were slowlycast into five 9-cm diameter Petri dishes, which had previously beentreated with a hydrophobic solution as described in U.S. Pat. No.6,395,331B1. Toluene was removed by evaporation in a vacuum oven (at apressure of ˜0.25 Torr or less) at 50° C. for about 6 hrs. The petridishes containing the dried SWCNT were then removed from the vacuumoven, and heated at 200° C. for 3 hrs in a conventional oven, and thencooled to ambient temperature. Five cohesive, free standing SWCNT waferswere obtained (FIG. 5). The wafers could be easily removed from thedishes, showing no adherence to the glass surface. The thickness of eachwafer was about 19 μm, as determined by SEM cross-sectional measurements(FIG. 6).

Example 12 Cohesive Adherent Film of SWCNT on Aluminum from TolueneSuspension

A dispersion of SWCNT in toluene was prepared as described in Example11. Aluminum foil with a thickness of about 25 μm was rinsed withacetone and dried with a stream of dry nitrogen gas to remove anysurface contaminants. A piece of foil large enough to cover the bottomand sides of a 9-cm Petri dish was placed inside such a dish with theshinier side face-up. The foil was shaped by hand by pressing it againstthe bottom and sides of the dish to create a foil lining inside thedish. A second dish was similarly lined with foil. About 43.5 g (50 ml)each of the SWCNT-toluene dispersion were slowly cast into the twoaluminum foil-lined Petri dishes (FIG. 7).

After removing toluene by evaporation in a vacuum oven (at a pressure of˜0.25 Torr or less) for about 6 hrs at 50° C., cohesive SWCNT films wereformed that adhered to the aluminum foil. The films did not delaminatefrom the foil either after drying, or after heating the films at 500° C.for 1 hr in ultra-high purity argon (<2 ppm oxygen). FIG. 8 shows thecohesive, adherent SWCNT films formed on aluminum foil substrates. FIG.9 shows a single cohesive, adherent SWCNT film on an aluminum foilsubstrate, deformed so that both sides are visible. The film did notdelaminate or lose adherence after deforming.

Example 13 Electrochemical Impedance Spectroscopy of Cohesive SWCNTAssemblies

Electrochemical Impedance Spectroscopy (EIS) measurements were performedon two cohesive SWCNT assemblies (wafers). One was an adherent SWCNTwafer on an aluminum (Al) substrate, prepared as described in Example12. The other was a free standing SWCNT wafer prepared as described inWO 2010/102250, using bromine as the dispersion solvent, which wassubsequently bonded to an Al current collector using a standardindustrial method. Both SWCNT wafers had a similar thickness of 16.5±1.5μm.

The EIS measurements were conducted at a DC bias of 2V with a sinusoidalsignal over a frequency range from 10 mHz to 0.1 MHz. The results weredisplayed on Nyquist plots of imaginary impedance (Z″) vs. realimpedance (Z′), shown in FIG. 10. In a typical Nyquist plot, the minimumZ′ value (at the bottom left of each data curve) represents theequivalent series resistance (ESR) of the device. The ESR is the resultof the combination of the contact resistance of the SWCNT-Al interface,the bulk resistance of the electrolyte solution, and the resistance ofAl itself.

Assuming the latter two contributions to ESR are approximately the samefor two devices of similar design and configuration, the difference inESR represents the difference in contact resistance of the SWCNT-Alinterface between the two devices.

The adherent SWCNT wafer on Al showed a significantly lower ESR of 0.36Ω, compared to ESR of 0.70 Ω for the free standing SWCNT wafer bonded toaluminum. This example demonstrates the clear advantage of applyingadherent cohesive SWCNT (or other carbon) assemblies directly toaluminum (or other metal) substrates, rather than producing freestanding assemblies and then bonding them to the metal. Namely, contactresistance between the assembly and the substrate was reduced byfabricating the adherent assembly directly on the metal substrate.

Although several embodiments of the invention have been described in theExamples given above, those of ordinary skill in the art will appreciatethat various modifications can be made without departing from the scopeof the invention. Accordingly, other embodiments are within the scope ofthe following claims.

What is claimed:
 1. A method of preparing a cohesive carbon assemblycomprising: (a) obtaining a carbon starting material in the form ofpowder, particles, flakes, or loose agglomerates, (b) dispersing thecarbon starting material in an organic solvent comprising toluene,o-dichlorobenzene (ODCB), isopropyl alcohol (IPA), N,N-dimethylformamide(DMF), benzene, chlorobenzene, m-dichlorobenzene,1,2,4-trichlorobenzene, bromobenzene, m-dibromobenzene,o-dibromobenzene, o-xylene, m-xylene, p-xylene, 1,2-dichloroethane,1,2-dibromoethane, chloroform, formamide, N-methylformamide,N-vinylformamide, N-(phenethyl)formamide, N,N-diethylformamide,N,N-bis(1-methylethyl)formamide, dimethyl sulfoxide, or any combinationthereof, in a prescribed ratio to form a dispersion, (c) applying thedispersion to a hydrophobic surface, and (d) substantially removing theorganic solvent in a controlled manner to form a cohesive carbonassembly on the hydrophobic surface, wherein the hydrophobic surfacecomprises a dimethyl organosilane, a fluorinated dimethyl organosilane,a fluorinated polymer, or Teflon.
 2. A method of preparing a cohesivecarbon assembly comprising: (a) obtaining a carbon starting material inthe form of powder, particles, flakes, or loose agglomerates, (b)dispersing the carbon starting material in an organic solvent comprisingtoluene, o-dichlorobenzene (ODCB), isopropyl alcohol (IPA),N,N-dimethylformamide (DMF), benzene, chlorobenzene, m-dichlorobenzene,1,2,4-trichlorobenzene, bromobenzene, m-dibromobenzene,o-dibromobenzene, o-xylene, m-xylene, p-xylene, 1,2-dichloroethane,1,2-dibromoethane, chloroform, formamide, N-methylformamide,N-vinylformamide, N-(phenethyl)formamide, N,N-diethylformamide,N,N-bis(1-methylethyl)formamide, dimethyl sulfoxide, or any combinationthereof, in a prescribed ratio to form a dispersion, (c) applying thedispersion to a hydrophobic surface, and (d) substantially removing theorganic solvent in a controlled manner to form a cohesive carbonassembly on the hydrophobic surface, wherein the dispersion is appliedto the hydrophobic surface by casting.
 3. A method of preparing acohesive carbon assembly comprising: (a) obtaining a carbon startingmaterial in the form of powder, particles, flakes, or looseagglomerates; (b) dispersing the carbon starting material in an organicsolvent comprising toluene, o-dichlorobenzene (ODCB), isopropyl alcohol(IPA), N,N-dimethylformamide (DMF), benzene, chlorobenzene,m-dichlorobenzene, 1,2,4-trichlorobenzene, bromobenzene,m-dibromobenzene, o-dibromobenzene, o-xylene, m-xylene, p-xylene,1,2-dichloroethane, 1,2-dibromoethane, chloroform, formamide,N-methylformamide, N-vinylformamide, N-(phenethyl)formamide,N,N-diethylformamide, N,N-bis(1-methylethyl) formamide, dimethylsulfoxide, or any combination thereof in a prescribed ratio to form adispersion; (c) applying the dispersion to a hydrophilic surface; and(d) substantially removing the organic solvent in a controlled manner toform a cohesive carbon assembly on the hydrophilic surface.
 4. Themethod of claim 3, wherein the hydrophilic surface is selected from thegroup consisting of metal, glass, silicon, plastic, ceramic, and anycombinations thereof.
 5. The method of claim 3, wherein the hydrophilicsurface is a metal substrate selected from the group consisting ofaluminum, nickel, copper, gold, silver, platinum, and any combinationthereof.
 6. The method of claim 3, wherein the dispersion is applied tothe hydrophilic surface by spin-coating, dip-coating, flow-coating,spray coating, casting, or any combination thereof.
 7. A cohesive carbonassembly on a metal substrate prepared by the method of claim
 5. 8. Thecohesive carbon assembly on a metal substrate of claim 7, wherein thecarbon starting material is carbon nanotubes, and the organic solvent iso-dichlorobenzene, toluene, IPA, DMF, or any combination thereof.
 9. Themethod of claim 3, wherein the carbon starting material is a carbonmaterial selected from the group consisting of carbon nanotubes,graphene, graphite, expanded graphite, exfoliated graphite, amorphouscarbon, and any combination thereof.
 10. The method of claim 9, whereinthe carbon nanotubes are single-walled carbon nanotubes, double-walledcarbon nanotubes, multi-walled carbon nanotubes, or any combinationthereof.
 11. The method of claim 10, wherein the Raman G/D ratio of theformed cohesive carbon assembly is about the same or greater than theRaman G/D ratio of the carbon starting material.
 12. The method of claim3, wherein the organic solvent is toluene, ODCB, IPA, DMF, or anycombination thereof.
 13. The method of claim 3, wherein the carbonstarting material is dispersed in the organic solvent in the presence ofmechanical agitation in step (b).
 14. The method of claim 13, whereinthe mechanical agitation comprises sonication, mechanical stirring, or acombination thereof.
 15. The method of claim 3, wherein the carbonstarting material is single-walled carbon nanotubes, the organic solventis toluene, ODCB, IPA, DMF, or any combination thereof, and the ratio ofcarbon starting material and the organic solvent is about 0.1 to about20 mg carbon per gram of the organic solvent.
 16. The method of claim 3,wherein the organic solvent is substantially free of a binding material.17. The method of claim 3, further comprising collecting the removedorganic solvent.
 18. The method of claim 1, wherein the carbon startingmaterial is a carbon material selected from the group consisting ofcarbon nanotubes, graphene, graphite, expanded graphite, exfoliatedgraphite, amorphous carbon, and any combination thereof.
 19. The methodof claim 18, wherein the carbon nanotubes are single-walled carbonnanotubes, double-walled carbon nanotubes, multi-walled carbonnanotubes, or any combination thereof.
 20. The method of claim 19,wherein the Raman G/D ratio of the formed cohesive carbon assembly isabout the same or greater than the Raman G/D ratio of the carbonstarting material.
 21. The method of claim 1, wherein the organicsolvent is toluene, ODCB, IPA, DMF, or any combination thereof.
 22. Themethod of claim 1, wherein the carbon starting material is dispersed inthe organic solvent in the presence of mechanical agitation in step (b).23. The method of claim 1, wherein the mechanical agitation comprisessonication, mechanical stirring, or a combination thereof.
 24. Themethod of claim 1, wherein the carbon starting material is single-walledcarbon nanotubes, the organic solvent is toluene, ODCB, IPA, DMF, or anycombination thereof, and the ratio of carbon starting material and theorganic solvent is about 0.1 to about 20 mg carbon per gram of theorganic solvent.
 25. The method of claim 1, wherein the organic solventis substantially free of a binding material.
 26. The method of claim 2,wherein the carbon starting material is a carbon material selected fromthe group consisting of carbon nanotubes, graphene, graphite, expandedgraphite, exfoliated graphite, amorphous carbon, and any combinationthereof.
 27. The method of claim 26, wherein the carbon nanotubes aresingle-walled carbon nanotubes, double-walled carbon nanotubes,multi-walled carbon nanotubes, or any combination thereof.
 28. Themethod of claim 27, wherein the Raman G/D ratio of the formed cohesivecarbon assembly is about the same or greater than the Raman G/D ratio ofthe carbon starting material.
 29. The method of claim 2, wherein theorganic solvent is toluene, ODCB, IPA, DMF, or any combination thereof.30. The method of claim 2, wherein the carbon starting material isdispersed in the organic solvent in the presence of mechanical agitationin step (b).
 31. The method of claim 30, wherein the mechanicalagitation comprises sonication, mechanical stirring, or a combinationthereof.
 32. The method of claim 2, wherein the carbon starting materialis single-walled carbon nanotubes, the organic solvent is toluene, ODCB,IPA, DMF, or any combination thereof, and the ratio of carbon startingmaterial and the organic solvent is about 0.1 to about 20 mg carbon pergram of the organic solvent.
 33. The method of claim 2, wherein theorganic solvent is substantially free of a binding material.